Coordination catalyst systems

ABSTRACT

The invention relates to the use of cyclic organometallic compounds as components in coordination catalyst systems, to corresponding coordination catalyst systems and also to processes for the preparation of polymers by coordination polymerization and of unsaturated hydrocarbons by catalyzed metathesis of alkenes and alkynes using such coordination catalyst systems.

BACKGROUND OF THE INVENTION

The invention relates to coordination catalyst systems based ontransition metal compounds of subgroups IV to VIII and organometalliccompounds of main group III of the Periodic Table of the Elements. Suchorganometallic catalysts are extraordinarily versatile catalyst systemswhich are used in chemical reactions of and with olefinicallyunsaturated compounds. These are, in particular, processes for preparingolefin polymers by coordination polymerization and the metathesis ofalkenes or alkynes. Of substantial industrial importance is thepreparation of polyethylene, of increased density (high densitypolyethylene, (HDPE) and of polymers and copolymers of ethylene,propylene or other 1-alkenes and alkynes. Catalyzed metathesis enableshigher unsaturated hydrocarbon compounds to be prepared in a targetedway from unsymmetric alkenes or alkynes and, from unsaturated cyclichydrocarbon compounds, makes it possible to obtain long-chainunsaturated hydrocarbons. The latter are used, for example, in thepreparation of elastomers. In addition, coordination catalysts are usedin further reactions, such as in the hydrogenation of alkenes or inorganometallic syntheses.

In accordance with the previous scientific knowledge of the mechanism ofaction of coordination catalysts, it is assumed that in each case onetransition metal compound forms the catalytically active center to whichthe olefinically unsaturated compound binds coordinately in a firststep. The olefin polymerization proceeds via a coordination of themonomers and a subsequent insertion reaction into a transitionmetal-carbon or a transition metal-hydrogen bond. The presence oforganometallic compounds in the coordination catalyst systems or duringthe catalyzed reaction is required to activate the catalyst or maintainits activity by reduction, with or without alkylation or formation of acomplex system. These compounds are therefore also known asco-catalysts. The compound containing the catalytically activetransition metal atom is known as the primary catalyst or pre-catalyst.

The best known industrially used catalyst systems for coordinationpolymerization are of the "Ziegler-Natta catalyst" type and of the"Phillips catalyst" type. The former comprise the reaction product of ametal alkyl or hydride of the elements of the first three main groups ofthe Periodic Table and a reducible compound of a transition metalelement of subgroups IV to VII, the combination most frequently usedcomprising an aluminum alkyl, such as triethylaluminum ordiethylaluminum chloride, and titanium(IV) chloride. Newer highly activeZiegler-Natta catalysts are systems in which the titanium compound ischemically fixed to the surface of magnesium compounds such as, inparticular, magnesium chloride.

As Phillips catalysts, use is made of chromium compounds which undergoreduction or activation principally by organometallic compounds and arebound to inorganic supports. Cr(VI) and Cr(II) are regarded ascatalytically active species ("reduced Phillips catalyst"). Here too,the co-catalysts used are principally alkylaluminum compounds and alsoaluminoxane compounds.

Newer developments of particularly high-performance polymerizationcatalysts are based on metallocene compounds. The catalysts known as"Kaminsky catalysts" are, for example, titanocene and zircononocenecompounds which are cyclopentadienyl complexes of titanium or zirconiumalkyls or halides and also derivatives thereof, which are activated withthe aid of aluminum, boron or phosphorus trialkyls or aluminoxane.

The practical use of these catalysts and related types in the widevariety of process variants developed can give products with sometimesvery different properties. For olefin polymers, which are of generallyknown importance as materials, usability and field of use depend as aresult of properties, on the one hand, on the type of monomers on whichthe polymer is based or on selection and ratio of the comonomers and thetypical physical parameters characterizing the polymer, such as meanmolecular weight, molecular weight distribution, degree of branching,degree of crosslinking, crystallinity, density, presence of functionalgroups in the polymer, etc., and, on the other hand, on propertiesdetermined by the process such as the content of low-molecular-weightimpurities, presence of catalyst residues and finally on the costs.

To assess the performance of a coordination catalyst system, thedecisive factors are, besides the realization of the desired productproperties, further factors such as the activity of the catalyst system,i.e. the amount of catalyst required for an economical conversion of agiven amount of olefin, the product throughput per unit time and theproduct yield, the loss of catalyst and also the reusability of thecatalyst. Catalyst systems are therefore sought which have as high aspossible a productivity but also have a high specificity in favor of alow degree of branching and a high stereo-regularity of the polymer, thelatter being particularly important for polypropylene and polymers ofhigher 1-alkenes.

However, an essential question is also that of the stability and thehandleability of the catalyst or its components. Pratically all knowncoordination catalysts are extremely sensitive to air and moisture.Exposure to (atmospheric) oxygen and/or water reduces or irreversiblydestroys the activity of known coordination catalysts. Reduced Phillipscatalysts, for example, immediately glow on exposure to air and are thenunusable. The coordination catalysts therefore have to be strictlyprotected from exposure to air and moisture during preparation, storageand use, which naturally makes handling more difficult and increases theoutlay required.

Conventional catalyst systems are also sensitive to materials whichcontain electron-rich elements such as oxygen or nitrogen. Compoundssuch as alcohols and amines, or even polar monomers which can be ofinterest as comonomers or additives for the polymer, deactivate thecatalyst.

Even more sensitive in this respect and therefore even more difficult tohandle are the organometallic compounds to be used as activators orcocatalysts, such as, in particular, the alkylaluminum compoundspredominantly used for this purpose. Precisely these pose a seriousproblem in practice because of their extreme sensitivity and pyrophoricnature.

There was therefore a particular need to find less sensitiveorganometallic compounds which are nevertheless suitable as activatingcomponents in coordination catalyst systems. These substitute compoundsshould be able to make coordination catalyst systems having at least thesame application properties and, if possible, an even greater breadth ofuse accessible. These themselves should in turn have a lower sensitivityand therefore less problematical handleability.

SUMMARY OF THE INVENTION

It has now been found that cyclic organometallic compounds of theformulae I or II ##STR1## in which M is B, Al, Ga, In,

X¹, X², X³ are, in each case independently of one another, CHR¹, NR², O,S,

Y¹, Y² are, in each case independently of one another, --(CH₂)_(m) --,o-(CH₂)_(p) --C₆ H₄ --(CH₂)_(q) --, o-(CH₂)_(p) --C₆ H₆ --(CH₂)_(q) --,o-(CH₂)_(p) --C₆ H₈ --(CH₂)_(q) --, o-(CH₂)_(p) --C₆ H₁₀ --(CH₂)_(q) --,o-(CH₂)_(p) --C₅ H₄ --(CH₂)_(q) --, o-(CH₂)_(p) --C₅ H₆ --(CH₂)_(q) --,o-(CH₂)_(p) --C₅ H₈ --(CH₂)_(q) --, --(CH₂)_(p) --CH═CH--(CH₂)_(q) --,

Z is NR³ R⁴, PR³ R⁴, OR⁵, SR⁵,

R¹ is H, OH, halogen, C₁₋₆ -alkyl or C₁₋₆ -alkoxy, C₅₋₇ -cycloalkyl,phenyl,

R², R³, R⁴, R⁵ are, in each case independently of one another, H or C₁₋₆-alkyl, C₅₋₇ -cycloalkyl, phenyl, R³ and R⁴ together also a C₄₋₆-alkylene bridge,

m is a number from 1 to 6,

p, q are, in each case independently of one another, a number from 0 to2, ##STR2## having M, R² and R³ as defined above and in which Z' is N,P,

a is a number from 2 to 4,

b, c are the numbers 0 or 1 with b+c=1,

are particularly suitable as components in coordination catalystsystems.

The invention accordingly provides for the use of cyclic organometalliccompounds of the formulae I or II as components in coordination catalystsystems.

The invention provides, in particular, for the use of these compounds ascomponents in coordination catalyst systems for the coordinationpolymerization and metathesis of alkenes and alkynes.

The invention further provides coordination catalyst systems based ontransition metal compounds of subgroups IV to VIII and organometalliccompounds of main group III of the Periodic Table of the Elements, withthese containing at least one compound of the formula I or II.

The invention additionally provides processes for preparing polymers bycoordination polymerization and for preparing unsaturated hydrocarboncompounds by a catalyzed metathesis reaction, in which processes thecoordination catalyst systems used are those containing at least onecompound of the formula I or II.

The compounds of the formulae I and II have a cyclic structure in whichthe group IIIa element boron (B), aluminum (Al), gallium (Ga) and indium(In) is in every case a member of a ring system.

In formula I, the group IIIa element M forms a metallocyclic ringtogether with the groups X¹, Y¹ and X². In the simplest case the ring isclosed by an alkylene group having a total of from 3 to 8 carbon atoms.The groups X¹ and X² adjacent to M can be an amino group, oxygen orsulfur. In other cases, Y¹ comprises an aromatic, an aliphatic or anunsaturated aliphatic ring having 5 or 6 carbon atoms and linked in theortho position or a C--C double bond preferably having a cisconfiguration. A carbon atom adjacent to the metal atom can also bear asubstituent R¹ which can be OH, halogen such as, in particular, F, Cland Br, C₁₋₆ -alkyl, C₁₋₆ -alkoxy, C₅₋₇ -cycloalkyl or phenyl. A carbonatom substituted in this way is then a center of chirality in themolecule. In such a case, formula I represents the racemic mixture andalso the corresponding enantiomers or diastereomers in their pure forms.The third bond of the metal atom M bears, linked via a spacer groupingX³ --Y², a group Z containing a heteroatom. X³ can be a CH₂ group, O, Sor an amino group optionally substituted by C₁₋₆ -alkyl, C₅₋₇-cycloalkyl or phenyl. Y² is, in the simplest case, an alkylene grouphaving from 1 to 6 carbon atoms. In the other cases, Y² comprises anaromatic, an aliphatic or an unsaturatedly aliphatic ring having 5 or 6carbon atoms and linked in the ortho position or a C--C double bondpreferably having a cis configuration. Z comprises the heteroatoms N, P,O or S in the form of an amino, a phosphino, hydroxy or thiol group, ineach case optionally substituted by C₁₋₆ -alkyl, with two such alkylradicals also being able to form an alkylene bridge, or C₅₋₇ -cycloalkylor phenyl.

In formula II, the metal atom M forms a monocyclic or bicyclic ringsystem via two or three alkylene bridges, which can each contain from 2to 4 carbon atoms, together with the heteroatom Z' which can be N or P.In the case of a monocyclic ring system, the bonds of M and Z' which arestill free in each case are occupied by H or C₁₋₆ -alkyl, C₅₋₇-cycloalkyl or phenyl.

The compounds of the formula I and II are stabilized intramolecularly byelectron transfer from the nitrogen, phosphorus, oxygen or sulfur atomto the electron-deficient IIIa element. In comparison with conventionalmetal alkyls, they therefore possess high stability towards(atmospheric) oxygen and moisture. They are not pyrophoric and thereforeeasy to handle. This stabilization is attributable to the intramolecularcoordinate bond.

Typical examples of compounds of the formula I are:

1-Alumina-1-(4-dimethylaminobutyl)cyclobutane

1-Alumina-1-(2-dimethylaminoethyl)cyclopentane

1-Alumina-1-(2-diethylaminoethyl)cyclopentane

1-Alumina-1-(2-dipropylaminoethyl)cyclopentane

1-Alumina-1-(2-diisopropylaminoethyl)cyclopentane

1-Alumina-1-(2-dibutylaminoethyl)cyclopentane

1-Alumina-1-(3-dimethylaminopropyl)cyclopentane

1-Alumina-1-(3-diethylaminopropyl)cyclopentane

1-Alumina-1-(3-dipropylaminopropyl)cyclopentane

1-Alumina-1-(3-diisopropylaminopropyl)cyclopentane

1-Alumina-1-(3-dibutylaminopropyl)cyclopentane

1-Alumina-1-(4-dimethylaminobutyl)cyclopentane

1-Alumina-1-(4-diethylaminobutyl)cyclopentane

1-Alumina-1-(4-dipropylaminobutyl)cyclopentane

1-Alumina-1-(4-diisopropylaminobutyl)cyclopentane

1-Alumina-1-(4-dibutylaminobutyl)cyclopentane

1-Alumina-1-(3-dimetylaminopropyl)-2-methylcyclopentane

1-Alumina-1-(2-dimethylaminoethyl)cyclohexane

1-Alumina-1-(2-diethylaminoethyl)cyclohexane

1-Alumina-1-(2-dipropylaminoethyl)cyclohexane

1-Alumina-1-(2-diisopropylaminoethyl)cyclohexane

1-Alumina-1-(2-dibutylaminoethyl)cyclohexane

1-Alumina-1-(3-dimethylaminopropyl)cyclohexane, b.p. 70°-73° C./0.01mbar

1-Alumina-1-(3-diethylaminopropyl)cyclohexane, b.p. 98° C./0.6 mbar

1-Alumina-1-(3-dipropylaminopropyl)cyclohexane

1-Alumina-1-(3-diisopropylaminopropyl)cyclohexane

1-Alumina-1-(3-dibutylaminopropyl)cyclohexane

1-Alumina-1-(4-dimethylaminobutyl)cyclohexane

1-Alumina-1-(4-diethylaminobutyl)cyclohexane

1-Alumina-1-(4-dipropylaminobutyl)cyclohexane

1-Alumina-1-(4-diisopropylaminobutyl)cyclohexane

1-Alumina-1-(4-dibutylaminobutyl)cyclohexane

1-Alumina-1-(o-diethylaminobenzyl)cyclopentane

1-Alumina-1-(o-diethylaminobenzyl)cyclohexane

1-Alumina-1-(o-diisopropylaminobenzyl)cyclohexane

1-Alumina-1-(3-dimethylaminopropyl)-2-methylcyclohexane

1-Alumina-1-(2-o-dimethylaminophenylethyl)cyclopentane

1-Alumina-1-(2-o-diethylaminophenylethyl)cyclobutane

1-Galla-1-(3-dimethylaminopropyl)cyclobutane

1-Galla-1-(2-dimethylaminoethyl)cyclopentane

1-Galla-1-(3-dimethylaminopropyl)cyclopentane

1-Galla-1-(2-dimethylaminoethyl)cyclopentane

1-Galla-1-(2-diethylaminoethyl)cyclopentane

1-Galla-1-(2-dipropylaminoethyl)cyclopentane

1-Galla-1-(2-diisopropylaminoethyl)cyclopentane

1-Galla-1-(2-dibutylaminoethyl)cyclopentane

1-Galla-1-(3-diethylaminopropyl)cyclopentane

1-Galla-1-(3-dipropylaminopropyl)cyclopentane

1-Galla-1-(3-diisopropylaminopropyl)cyclopentane

1-Galla-1-(3-dibutylaminopropyl)cyclopentane

1-Galla-1-(4-dimethylaminobutyl)cyclopentane

1-Galla-1-(4-diethylaminobutyl)cyclopentane

1-Galla-1-(4-dipropylaminobutyl)cyclopentane

1-Galla-1-(4-isopropylaminobutyl)cyclopentane

1-Galla-1-(4-dibutylaminobutyl)cyclopentane

1-Galla-1-(3-dimethylaminopropyl)cyclohexane, b.p. 67° C./0.1 mbar

1-Galla-1-(3-diethylaminopropyl)cyclohexane, b.p. 94° C./0.01 mbar

1-Galla-1-(3-dipropylaminopropyl)cyclohexane

1-Galla-1-(3-diisopropylaminopropyl)cyclohexane

1-Galla-1-(3-dibutylaminopropyl)cyclohexane

1-Galla-1-(2-dimethylaminoethyl)cyclohexane

1-Galla-1-(2-diethylaminoethyl)cyclohexane

1-Galla-1-(2-dipropylaminoethyl)cyclohexane

1-Galla-1-(2-diisopropylaminoethyl)cyclohexane

1-Galla-1-(2-dibutylaminoethyl)cyclohexane

1-Galla-1-(4-dimethylaminobutyl)cyclohexane, b.p. 138° C./0.01 mbar

1-Galla-1-(4-diethylaminobutyl)cyclohexane

1-Galla-1-(4-dipropylaminobutyl)cyclohexane

1-Galla-1-(4-isopropylaminobutyl)cyclohexane

1-Galla-1-(4-dibutylaminobutyl)cyclohexane

1-Galla-1-(o-dimethylaminobenzyl)cyclobutane

1-Galla-1-(o-dimethylaminobenzyl)cyclopentane

1-Galla-1-(o-dimethylaminobenzyl)cyclohexane

1-Galla-1-(o-diethylaminobenzyl)cyclohexane

1-Galla-1-(o-dipropylaminobenzyl)cycloheptane

1-Inda-1-(2-diethylaminoethyl)cyclobutane

1-Inda-1-(2-dimethylaminoethyl)cyclopentane

1-Inda-1-(2-diethylaminoethyl)cyclopentane

1-Inda-1-(2-dipropylaminoethyl)cyclopentane

1-Inda-1-(2-diisopropylaminoethyl)cyclopentane

1-Inda-1-(2-dibutylaminoethyl)cyclopentane

1-Inda-1-(3-dimethylaminopropyl)cyclopentane

1-Inda-1-(3-diethylaminopropyl)cyclopentane

1-Inda-1-(3-dipropylaminopropyl)cyclopentane

1-Inda-1-(3-diisopropylaminopropyl)cyclopentane

1-Inda-1-(3-dibutylaminopropyl)cyclopentane

1-Inda-1-(4-dimethylaminobutyl)cyclopentane

1-Inda-1-(4-diethylaminobutyl)cyclopentane

1-Inda-1-(4-dipropylaminobutyl)cyclopentane

1-Inda-1-(4-diisopropylaminobutyl)cyclopentane

1-Inda-1-(4-dibutylaminobutyl)cyclopentane

1-Inda-1-(2-dimethylaminoethyl)cyclohexane,

1-Inda-1-(2-diethylaminoethyl)cyclohexane,

1-Inda-1-(2-dipropylaminoethyl)cyclohexane

1-Inda-1-(2-diisopropylaminoethyl)cyclohexane

1-Inda-1-(2-dibutylaminoethyl)cyclohexane

1-Inda-1-(3-dimethylaminopropyl)cyclohexane

1-Inda-1-(3-diethylaminopropyl)cyclohexane

1-Inda-1-(3-dipropylaminopropyl)cyclohexane

1-Inda-1-(3-diisopropylaminopropyl)cyclohexane

1-Inda-1-(3-dibutylaminopropyl)cyclohexane

1-Inda-1-(4-dimethylaminobutyl)cyclohexane,

1-Inda-1-(4-diethylaminobutyl)cyclohexane

1-Inda-1-(4-dipropylaminobutyl)cyclohexane

1-Inda-1-(4-diisopropylaminobutyl)cyclohexane

1-Inda-1-(4-dibutylaminobutyl)cyclohexane

1-Inda-1-(o-diisopropylaminobenzyl)cyclobutane

1-Inda-1-(o-dimethylaminobenzyl)cyclopentane

1-Inda-1-(o-dibutylaminobenzyl)cyclopentane

1-Inda-1-(o-dimethylaminobenzyl)cyclohexane

1-Inda-1-(o-diethylaminobenzyl)cyclohexane

1-Inda-1-(o-dimethylaminobenzyl)cyclooctane

2,5-Dimethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1aluminacyclopentane

2,5-Dimethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-aluminacyclohexane

2,5-Dimethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-aluminacycloheptane

2,5-Dimethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-aluminacyclopentane

2,5-Dimethyl-1-(3-diethylaminopropyl)-2,5-diaza-1-aluminacyclohexane

2,5-Dimethyl-1-(3-diethylaminopropyl)-2,5-diaza-1-aluminacycloheptane

2,5-Diethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-aluminacyclohexane

2,5-Diethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-aluminacyclopentane

2,5-Diethyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-aluminacyclohexane

2,5-Diethyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-aluminacyclopentane

2,5-Diethyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-aluminacycloheptane

2-Ethyl-5-propyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-aluminacyclohexane

2-Ethyl-5-propyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-aluminacyclopentane

2-Ethyl-5-propyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-aluminacycloheptane

2,5-Dimethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-gallacyclopentane,b.p. 220° C./0.1 mbar

2,5-Dimethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-gallacyclohexane

2,5-Dimethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-gallacycloheptane

2,5-Dimethyl-1-(3-diethylaminopropyl)-2,5-diaza-1-gallacyclopentane

2,5-Dimethyl-1-(3-diethylaminopropyl)-2,5-diaza-1-gallacyclohexane

2,5-Dimethyl-1-(3-diethylaminopropyl)-2,5-diaza-1-gallacycloheptane

2,5-Diethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-gallacyclohexane

2,5-Diethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-gallacyclopentane

2,5-Diethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-gallacycloheptane

2,5-Diethyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-gallacyclohexane

2,5-Diethyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-gallacyclopentane

2,5-Diethyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-gallacycloheptane

2-Ethyl-5-propyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-gallacyclohexane

2-Ethyl-5-propyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-gallacyclopentane

2-Ethyl-5-propyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-gallacycloheptane

2,5-Dimethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-indacyclopentane

2,5-Dimethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-indacyclohexane

2,5-Dimethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-indacycloheptane

2,5-Dimethyl-1-(3-diethylaminopropyl)-2,5-diaza-1-indacyclopentane

2,5-Dimethyl-1-(3-diethylaminopropyl)-2,5-diaza-1-indacyclohexane

2,5-Dimethyl-1-(3-diethylaminopropyl)-2,5-diaza-1-indacycloheptane

2,5-Diethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-indacyclohexane

2,5-Diethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-indacyclopentane

2,5-Diethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-indacycloheptane

2,5-Diethyl-1-(3-dimethylaminobutyl)-2,5-diaza-1-indacyclohexane

2,5-Diethyl-1-(3-dimethylaminobutyl)-2,5-diaza-1-indacyclopentane

2,5-Diethyl-1-(3-dimethylaminobutyl)-2,5-diaza-1-indacycloheptane

2-Ethyl-5-propyl-1-(4-dimethylaminobutyl)-2,5-diaza-1indacyclohexane

2-Ethyl-5-propyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-indacyclopentane

2-Ethyl-5-propyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-indacycloheptane

Typical examples of compounds of the formula II are:

5-Methyl-1-galla-5-azacyclooctane, m.p. -22° C.

1,5-Dimethyl-1-galla-5-azacyclooctane, b.p. 83° C./12 mbar

1,5-Diethyl-1-galla-5-azacyclooctane

1,5-Dipropyl-1-galla-5-azacyclooctane

1,5-Dimethyl-1-alumina-5-azacyclooctane, b.p. 76° C./4 mbar

1,5-Diethyl-1-alumina-5-azacyclooctane, b.p. 71° C./0.6 mbar

1,5-Diisopropyl-1-alumina-5-azacyclooctane

1,5-Dibutyl-1-alumina-5-azacyclooctane

1-Methyl-5-ethyl-1-galla-5-azacyclooctane

1-Ethyl-5-methyl-1-alumina-5-azacyclooctane, b.p. 71° C./0.6 mbar

1,6-Dimethyl-1-galla-6-azacyclodecane

1,6-Dimethyl-1-alumina-6-azacyclodecane

1,6-Diethyl-1-galla-6-azacyclodecane

1,4-Dimethyl-1-galla-4-azacyclohexane

1,6-Diethyl-1-alumina-6-azacyclodecane

1-Galla-5-azabicyclo[3.3.3]undecane, m.p. 54° C.

1-Galla-4-azabicyclo[2.2.2]octane,

1-Alumina-5-azabicyclo[3.3.3]undecane, b.p. 80° C./0.4 mbar

1-Alumina-4-azabicyclo[2.2.2]octane

1-Galla-6-azabicyclo[4.4.4]tetradecane

1-Alumina-6-azabicyclo[4.4.4]tetradecane

1,5-Dimethyl-1-inda-5-azacyclooctane, b.p. 38° C./0.05 mbar

1,5-Diethyl-1-inda-5-azacyclooctane

1,5-Dipropyl-1-inda-5-azacyclooctane

1,5-Diisopropyl-1-inda-5-azacyclooctane

1,5-Dibutyl-1-inda-5-azacyclooctane

1-Methyl-5-ethyl-1-inda-5-azacyclooctane

1-Ethyl-5-propyl-1-inda-5-azacyclooctane

1,6-Dimethyl-1-inda-6-azacyclodecane

1,6-Diethyl-1-inda-6-azacyclodecane

1,4-Dimethyl-1-inda-4-azacyclohexane

1-Inda-5-azabicyclo[3.3.3]undecane

1-Inda-4-azabicyclo[2.2.2]octane

1-Methyl-5-cyclohexyl-1-inda-5-azacyclooctane

1-Methyl-5-phenyl-1-inda-5-azacyclooctane

1-Inda-6-azabicyclo[4.4.4]tetradecane

1,6-Dimethyl-1-galla-6-azacyclodecane

1,6-Diethyl-1-galla-6-azacyclodecane

1,6-Dipropyl-1-galla-6-azacyclodecane

1,6-Diisopropyl-1-galla-6-azacyclodecane

1,6-Dibutyl-1-galla-6-azacyclodecane

1,6-Di-tert-butyl-1-galla-6-azacyclodecane

1,6-Diisobutyl-1-galla-6-azacyclodecane

1,4-Dimethyl-1-galla-4-azacyclohexane

1,4-Diethyl-1-galla-4-azacyclohexane

1,4-Dipropyl-1-galla-4-azacyclohexane

1,4-Diisopropyl-1-galla-4-azacyclohexane

1,4-Dibutyl-1-galla-4-azacyclohexane

1,4-Diisobutyl-1-galla-4-azacyclohexane

1,4-Di-tert-butyl-1-galla-4-azacyclohexane

1-Methyl-5-ethyl-1-galla-5-azacyclooctane

1-Methyl-5-propyl-1-galla-5-azacyclooctane

1-Propyl-5-methyl-1-galla-5-azacyclooctane, b.p. 86° C./0.01 mbar

1-Ethyl-5-methyl-1-galla-5-azacyclooctane, b.p. 64° C./1 mbar

1-Ethyl-6-propyl-1-galla-6-azacyclodecane

1-Propyl-6-butyl-1-galla-6-azacyclodecane

1-Methyl-6-ethyl-1-galla-6-azacyclodecane

1-Methyl-4-ethyl-1-galla-4-azacyclohexane

1-Propyl-4-methyl-1-galla-4-azacyclohexane

1-Ethyl-4-butyl-1-galla-4-azacyclohexane

Preference is given to organoaluminum compounds of the formulae I andII.

Particularly preferred are the compounds1-alumina-1-(3-dimethylaminopropyl)cyclohexane and1,5-dimethyl-1-alumina-5-azacyclooctane.

Most of the cyclic organometallic compounds of the formulae I and II areas such already known per se. Thus, compounds of the formula I have beendescribed for the first time in DE 3817090 and in DE 4009394 andcompounds of the formula II have been described for the first in DE3726485. It can already be seen from the specified documents that thecompounds are stable towards air and moisture.

However, they are only proposed for use in the production of thin metalor compound semiconductor layers by gas phase deposition. Thesedocuments make no reference to the suitability of these compounds asactivating components in coordination catalyst systems for olefinpolymerization or metathesis.

The compounds of the formulae I and II are prepared by methods known perse, as described in the literature (e.g. G. Bahr, P. Burba, Methoden derOrganischen Chemie, Vol. XIII/4, Georg Thieme Verlag, Stuttgart (1970)),namely under reaction conditions which are known and suitable for thespecified reactions. For this purpose, use can also be made of variantsknown per se and not mentioned here.

Thus these compounds can be prepared, for example, by reactingalkylmetal chlorides with an alkali metal organo-compound of thecorresponding Lewis base or a Grignard compound in an inert solvent.

Further details of the synthesis of these compounds can be taken fromthe abovementioned patent documents or Chem. Ber. 124, 1113-1119 (1991).

Coordination catalyst systems which contain the cyclic organometalliccompounds of the formulae I and II of the invention are particularlysuitable for the polymerization of 1-alkenes and 1-alkynes, with itbeing possible to obtain both homopolymers from uniform monomers andcopolymers from monomer mixtures. They are furthermore suitable for themetathesis of 1-alkenes and 1-alkynes and for the ring-openingmetathesis of cyclic alkenes.

In the use according to the invention of the compounds of the formulae Iand II as activating components in coordination catalyst systems, it hassurprisingly been found that as a result the catalyst systems are lesssensitive to (atmospheric) oxygen and moisture, so that it is notnecessary to take such strict protective measures as are required forcoordination catalysts activated with conventional aluminum alkyls. Thisfinding is particularly surprising and not foreseeable, especially sincethe use of structurally similar, but non-cyclic organoaluminumcompounds, such as, for example,(3-diethylaminopropyl)di-isobutylaluminum, is already known in certaincoordination catalyst systems. U.S. Pat. No. 3,154,528 disclosescoordination catalyst systems based on vanadium tetrachloride andactivated with such non-cyclic compounds, which catalyst systems are,however, described as being just as air and moisture sensitive as theconventional coordination catalyst systems. JP 60-240706, JP 61-007305,JP 61-252205, JP 62-100505 and JP 62-138506 disclose coordinationcatalyst systems based on titanium compounds, which likewise containsuch non-cyclic organoalminum compounds and also further compoundsfunctioning as electron donors, which, however, are first activated withconventional aluminum alkyls. Owing to the presence of the latter, thesecatalyst systems are likewise extremely sensitive and require the usualstrict protective measures.

Our own investigations using these known noncyclic organoaluminumcompounds in Ziegler-Natta and Phillips catalyst systems also confirmthat these definitely require activation with conventional aluminumalkyls to obtain an olefin polymer at all or at least usable productyields.

In the coordination catalyst systems of the invention, an additionalactivation by aluminum alkyls or other activators is not required.

In the coordination catalyst systems of the invention, moderate exposureto air, oxygen or moisture does not result in destruction or a drasticreduction in activity. Corresponding coordination catalyst systems basedon supported chromium do not glow, for example, in air, but continue tobe as usable as before. This has the very advantageous consequence thatthe handling of the coordination catalyst systems of the invention issubstantially less problematical in preparation, storage and use. Thecomplicated exclusion of even traces of air, oxygen and moisture fromthe solvents, monomers and protective gases used in the polymerizationcan therefore be omitted.

In addition, the compounds of the formulae I and II to be used accordingto the invention in coordination catalyst systems give furtheradvantageous results in the intended use in polymerization processes andmetathesis reactions. Thus, the corresponding coordination catalystsystems according to the invention generally show an extremely highactivity. This has the consequence that more product is formed with theamount of catalyst used or the required amount of catalyst can becorrespondingly reduced. Advantageous consequences of this are thatcorrespondingly less catalyst has to be separated off from the productor products having a lower residual catalyst content are obtained and,not least, the costs are also reduced because of lower catalystconsumption. Naturally, numerous further factors also have an influencehere, such as the qualitative and quantitative composition of thecatalyst systems, the nature of the monomers or the composition ofmonomer mixtures used in copolymerization, reaction conditions andoperating procedure in the polymerization. However, those skilled in theart can easily determine and optimize the most suitable catalyst systemfor their purposes with the aid of routine experiments. Thus, forexample, a ZieglerNatta catalyst system based on Ti/MgCl₂ which had beenactivated with the compound1-alumina-1-(3-dimethylaminopropyl)cyclohexane as cocatalyst showed anoptimum in respect of constant activity and product yield in thepolymerization of ethylene on an industrial scale when the molar ratioof Ti to Al in the catalyst system was in the range 1:40-50.

Furthermore, for the coordination catalyst systems of the invention inolefin polymerization, there is found a pronounced specificity in thedirection of high molecular weights and narrow molecular weightdistributions. These findings too are dependent on factors such as thecomposition of the catalyst system, the nature of the monomers andprocess conditions used, but can easily be optimized for the particularapplication. Thus, for example, in the polymerization of 1-octene and1-decene using Phillips catalyst systems based on Cr/SiO₂ which had beenactivated with 1-alumina-1-(3-dimethylaminopropyl)cyclohexane ascocatalyst, with variation of the molar ratio of Cr to Al in the rangefrom 1:0.5 to 1:4, high product yields and high molecular weights wereobtained throughout and for 1-octene there was an optimum in respect ofa narrow molecular weight distribution at a ratio of Cr to Al of 1:1.

A further advantageous finding which has emerged is that Phillipscatalysts activated with compounds of the formulae I and II do not, asis otherwise usual, stick together with the polymer and remain adheringto the reaction apparatus, which makes the removal and separationconsiderably easier.

Metathesis catalysts based on Mo/SiO₂ activated with1-alumina-1-(3-dimethylaminopropyl)cyclohexane show a surprisingly highproduct specificity. Thus, for example, the metathesis of 1-octene usingthe specified catalyst system gave exclusively the desired C₁₄ -alkene,while a catalyst system of this type activated with triisobutylaluminumgave, besides the desired product, a high proportion of byproduct in theform of a C₂ - to C₂₀ -alkene mixture.

In the polymerization of 1-alkenes, the catalysts of the invention can,if the situation arises, act in a pronounced stereoselective way to giveisotactic polymers. In metathesis or ring-openingmetathesis-polymerization, particular stereoisomers or products having aparticular configuration can be preferentially formed. Thisstereoselectivity can be additionally influenced by targeted structuringof the compounds of the formula I and II, in particular on their cyclicstructural elements. If, for example, in formula I it is the case thatX¹ and/or X² are CHR¹, the radical R¹ not being hydrogen, then thecyclic structural element has an asymmetric carbon atom and thus acenter of chirality which can effect stereoselective induction inpolymerization or metathesis of 1-alkenes. Such a stereoselective oroptionally enantioselective induction by a corresponding catalyst systemis preferably to be expected when the compounds of the formula I areused in enantiomerically or diastereomerically pure form.

The Ziegler-Natta and the Phillips polymerization of ethylene andpropylene is successful without problems using the coordination catalystsystems of the invention even under mild conditions, such as, forexample, at about 70° C. and under a pressure of 8-10 bar. In comparisonwith activation using conventional aluminum alkyls, such as, forexample, triisobutylaluminum, this achieves predominantly higher productyields and, in particular, significantly higher molecular weights.Olefin polymers having a particularly high molecular weight, for exampleabove 10⁶, as are easily obtainable on a laboratory scale and withouttechnical optimization using the catalyst systems of the invention, areof great industrial importance.

Coordination catalyst systems of the "Ziegler-Natta" type and of the"Phillips" type which are activated with the compounds of the formulae Iand II of the invention as cocatalysts additionally show the surprisingproperty that they can also be used to polymerize polar olefinicallyunsaturated monomers. It is known that conventional catalyst systemsessentially allow only 1-alkenes and 1-alkynes to be polymerized.Styrene, for example, hardly undergoes coordination polymerization andeven more polar monomers such as vinyl compounds and acrylic acidderivatives do not undergo coordination polymerization at all.Presumably this is because these polar compounds deactivate the metalatoms of the primary catalyst and/or cocatalyst by means of a strongcoordinate bond. However, as a result of the intramolecular coordinatesaturation, this is no longer possible in the compounds of the formulaeI and II, which explains the notable activity of the catalyst systems ofthe invention towards polar monomers.

The use according to the invention of the compounds of the formulae Iand II as activating components in coordination catalyst systems iscarried out completely analogously to and in substitution of thehitherto customary organometallics and, in particular, the extremelysensitive and dangerous aluminum alkyls. Owing to the increasedactivity, both the proportion of organometallic compound in the catalystsystem and the amount of catalyst in the reaction can be reduced. Thepreparation and use of the catalysts is carried out in a manner knownper se as is customary for the particular system and the particular use.In general, olefin polymerization and metathesis are carried out usingheterogeneous catalysis in the suspension process. For this purpose, thesupported pre-catalyst is first prepared from the catalytically activetransition metal compound and a finely divided support material, thisprecatalyst is, if required, activated or preactivated in a conventionalmanner and then suspended in a solvent, for example in an alkanehydrocarbon such as pentane or hexane. The addition of the cocatalyst iscarried out, as is also customary otherwise, directly prior to thereaction of the monomers or "in situ" in the presence of the same. Thecontrol of the reaction and also the isolation and workup of thereaction products is likewise carried out in a completely analogous way.As already mentioned, owing to the stability of the compounds of theformulae I and II and the lower sensitivity of the resulting catalystsystems, all these procedures can be carried out with substantiallyfewer problems and with substantially fewer strict protective and safetymeasures.

The invention thus makes accessible novel coordination catalyst systemshaving advantageous properties and also a considerably expanded breadthof use, which catalyst systems can additionally be tailored to therespective requirements of the application.

In the following examples, all handling, if not otherwise indicated, iscarried out under a protective gas atmosphere (N₂, Ar) andwith-exclusion of moisture.

EXAMPLE 1

0.25 mol of magnesium turnings, activated by iodine, are initiallycharged in 100 ml of diethyl ether. After addition of 0.06 mol of1,5-dibromopentane at room temperature, the mixture is heated for 3hours under reflux.

The Grignard solution decanted off from the magnesium and 0.06 mol of3-dimethylaminopropylaluminum dichloride, dissolved in 150 ml of ether,are synchronously combined and reacted with vigorous stirring.

Subsequently the reaction mixture is stirred at room temperature. Thevolatile constituents are distilled off at a bath temperature of up to180° C. and a pressure of 10-2 mbar and again fractionally distilled.

1-Alumina-1-(3-dimethylaminopropyl)cyclohexane is obtained as awater-white, air-stable liquid having a boiling point of 98°/0.6 mbar.

EXAMPLE 2

2.9 g (119 mmol) of magnesium grit are initially charged in 100 ml ofTHF and heated under reflux. 10 g (54 mmol) ofmethylbis(3,3'-chloropropyl)amine, dissolved in 40 ml of THF, are added.Subsequently the mixture is heated for a further 2 hours under reflux.

At room temperature, 5.7 g (50 mmol) of methyl-aluminum dichloride in 20ml of THF are added to the Grignard solution. The mixture is stirred for24 hours at room temperature and then heated for 3 hours under reflux.The solution is decanted off from the precipitated MgCl₂ and, afterdrawing off the solvent, 1,5-dimethyl-1-alumina-5-azacyclooctane isobtained by vacuum distillation as a clear, stable liquid having aboiling point of 71°/0.6 mbar.

EXAMPLE 3

3.6 g (148 mmol) of magnesium grit are initially charged in 100 ml ofTHF and heated under reflux. 12 g (49 mmol) of3-chloro-N,N-bis(3-chloropropyl)propan-1-amine in 40 ml of THF areadded, and the mixture is heated for a further 2 hours.

At room temperature, 6.6 g (47 mmol) of aluminum trichloride in 20 ml ofTHF, are added to the Grignard solution. The mixture is stirred for 24hours at room temperature and is then heated for 4 hours under reflux.After distilling off the solvent and purification by vacuumdistillation, 1-alumina-5-azabicyclo[3.3.3]undecane is obtained as aclear, stable liquid having a boiling point of 80°/0.4 mbar.

EXAMPLE 4 Supported Cr(VI) pre-catalyst

1,000 g of silica gel (particle size 200-500 mm) are boiled for 45minutes in 3,000 ml of distilled H₂ O, washed three times with hot H₂ Oand dried for 15 hours at 115° C./75 mbar. This material is subsequentlyslurried in a solution of 46 g of CrO₃ in 200 ml of water, stirred for30 minutes, filtered off and dried at 70° C./75 mbar for 12 hours andthen for 2 hours at 115/75 mbar. The product is then heated in a streamof oxygen (fluidized bed or rotary tube) to 800° C. over the course of 6hours and left at this temperature for 1 hour. After cooling to 350° C.,the oxygen is replaced by argon. The catalyst contains about 1% ofCr(VI).

EXAMPLE 5 Supported Cr(II) Pre-catalyst

First, the procedure of Example 4 is repeated. However, argon is thendisplaced by CO; the reduction is carried out in the CO stream at 350°C./60 min. Finally, the CO is again replaced by argon and the materialis cooled to room temperature. The catalyst contains about 0.84% ofCr(II).

EXAMPLE 6 Supported Mo(VI) Pre-catalyst

1.67 mmol of MoO₂ -acetylacetonate complex are dissolved in 30 ml of CH₂Cl₂ and applied to 9 g of silica gel (particle size 200-500 mm).Subsequently the material is washed with CH₂ Cl₂ and dried at -10° C. ina high vacuum.

EXAMPLE 7 Polymerization of 1-octene Over Cr(VI)

In parallel batches, the pre-catalyst of Example 4 is suspended inn-pentane and admixed with differing amounts of the compound of Example1 as cocatalyst. Subsequently, 1-octene is added in the ratioCr:1-octene of 1:100 and the mixture is shaken for 24 hours at 20° C.The catalyst is filtered off and washed with n-pentane. The pentaneeluates are evaporated. The polymer product is analyzed by IR and ¹³C-NMR spectroscopy and by gel permeation chromatography (polystyrenestandard). Table 1 shows the results.

                  TABLE 1                                                         ______________________________________                                        Cr:Al   Yield in %    M.sub.w D = M.sub.w /M.sub.n                            ______________________________________                                        1:0.5   55            10,900  8.45                                            1:1     86            21,900  6.35                                            1:1.5   67            15,650  9.1                                             1:2     43            14,900  8.4                                             ______________________________________                                    

Throughout, high molecular weights (M_(w)) with narrow molecular weightdistributions (D=M_(w) /M_(n)) were obtained together with good yields.The catalyst having Cr:Al=1:1 gave optimum results.

EXAMPLE 8 Polymerization of 1-octene Over Cr(II)

The procedure of Example 7 is repeated using the pre-catalyst of Example5. Table 2 shows the results.

                  TABLE 2                                                         ______________________________________                                        Cr:Al   Yield in %    M.sub.w D = M.sub.w /M.sub.n                            ______________________________________                                        1:1     91            37.900  2.1                                             1:2     77            62,800  11.0                                            1:4     68            78,700  7.9                                             Comparative experiment using triethylaluminum as cocatalyst                     1:2.7 52            31,800  broad/bimodal                                   ______________________________________                                    

EXAMPLE 9 Polymerization of 1-decene Over Cr(II)

The procedure of Example 8 is repeated using 1-decene. Table 3 shows theresults.

                  TABLE 3                                                         ______________________________________                                        Cr:Al   Yield in %    M.sub.w D = M.sub.w /M.sub.n                            ______________________________________                                        1:2     83            47,200   9.8                                            1:3     97            77,700  11.6                                            1:4     85            53,200  14.5                                            ______________________________________                                    

EXAMPLE 10 Metathesis of 1-octene Over Mo(VI)

In parallel batches, 300 mg in each case of the pre-catalyst of Example6 (corresponding to 0.05 mmol of Mo) are admixed with 1-octene in aratio Mo:1-octene of 1:2,500 and differing amounts of the compound ofExample 1 are added as cocatalyst. The mixture is allowed to react for24 hours at 122° C. The conversion of 1-octene and the tetradecene (C₁₄)formed and any byproducts are determined by gas chromatography.

In an analogous comparative experiment, triisobutylaluminum (TIBA) isused as cocatalyst. Table 4 shows the results.

                  TABLE 4                                                         ______________________________________                                                   Yield in % Yield in %                                              Mo:Al      Product C.sub.14                                                                         Byproducts C.sub.2 -C.sub.20                            ______________________________________                                        1:2        14.8       --                                                      1:4        19.4       --                                                       1:10       4.8       --                                                      Comparative experiment using TIBA                                             1:4        12.3       16.2                                                    ______________________________________                                    

EXAMPLE 11 Polymerization of 1-octene Over Cr(II) With and WithoutAdmission of Oxygen

The procedure of Example 8 is repeated. In a parallel batch, 5 ml of O₂gas is injected by means of a syringe prior to the addition of thealkene. Table 5 shows the results.

                  TABLE 5                                                         ______________________________________                                        Cr:Al   Yield in %                                                                              M.sub.w        D = M.sub.w /M.sub.n                         ______________________________________                                                          Addition of O.sub.2                                         1:3     73        76,500         13.4                                                           No addition of O.sub.2                                      1:3     87        78,700          7.9                                         ______________________________________                                    

The result verifies that the addition of O₂ exercises no substantialinfluence on the activity of the catalyst system.

EXAMPLE 12 Polymerization of Ethylene Over Cr(VI)

In parallel batches, 200 mg in each case of precatalyst of Example 4 aresuspended in n-heptane in an autoclave. To this are added differingamounts of the compound of Example 1 or, for comparison, of cocatalystsof the prior art, and at a temperature of 70° C. ethylene is then fed inunder a pressure of 10 bar. After 24 hours the mixture is worked up inthe usual way. Table 6 shows the results.

                  TABLE 6                                                         ______________________________________                                              Yield                                                                   Cr:Al g polymer/g Cr · h                                                                 m.p. °C.                                                                        M.sub.w                                                                              Appearance                                ______________________________________                                        1:0      0          --       --     no polymer                                1:1   1,700         189-192  1.02 · 10.sup.6                                                             white, finely                                                                 particulate                                                                   polymer                                   1:5   1,250         175-200  1.03 · 10.sup.6                                                             white, finely                                                                 particulate                                                                   polymer                                   1:10  1,300         188-194   1.2 · 10.sup.6                                                             white, finely                                                                 particulate                                                                   polymer                                   1:15  1,400         191-195  1.1 · 10.sup.6                                                              white, finely                                                                 particulate                                                                   polymer                                   Comparative experiments using TIBA                                            1:1   1,200         185-188   8.5 · 10.sup.5                                                             white, finely                                                                 particulate                                                                   polymer                                   1:15  1,500         174-177   5.9 · 10.sup.5                                                             white, finely                                                                 particulate                                                                   polymer                                   Comparative experiment using                                                  (2-dimethylaminoethoxy)dimethylaluminum                                       1:25     0          --       --     no polymer                                ______________________________________                                    

The cocatalyst of the invention effects excellent yields and, incomparison with TIBA, an increase in the molecular weight. Thenon-cyclic compound effects no polymerization.

EXAMPLE 13 Ziegler-Natta Polymerization of Ethylene

In parallel batches, 50 mg in each case of TiCl₄ are suspended inn-heptane in an autoclave and differing amounts of the compound ofExample 1 or, for comparison, of cocatalysts of the prior art are added.At a temperature of 70° C., ethylene is then fed in under a pressure of8-10 bar and the reaction is stopped after one hour. Table 7 shows theresults

                  TABLE 7                                                         ______________________________________                                              Yield                                                                   Ti:Al g polymer/g Ti · h                                                                 m.p. °C.                                                                        M.sub.w                                                                              Appearance                                ______________________________________                                        1:3   14,700        175-210  7.9 · 10.sup.6                                                              finely                                                                        particulate,                                                                  white                                     1:5   15,400        190        2 ·10.sup.6                                                               finely                                                        (decom-         particulate,                                                  position)       white                                     Comparative experiment using TIBA                                             1:3   18,600        196-205  3.4 · 10.sup.5                                                              coarsely                                                                      particulate,                                                                  gray                                      Comparative experiment using                                                  (3-dimethylaminopropyl)diisopropylaluminum                                    1:5      0          --       --     no polymer                                Comparative experiment using                                                  (2-dimethylaminoethoxy)dimethylaluminum                                       1:5   --            --       --     traces of                                                                     polymer                                   ______________________________________                                    

The cocatalyst of the invention effects excellent yields and, incomparison with TIBA, an increase in the molecular weight. Thenon-cyclic compounds effect no polymerization or only traces ofpolymerization.

EXAMPLE 14 Industrial Ziegler-Natta Polymerization of Ethylene

The polymerization of ethylene is carried out by the suspension processin n-heptane at a constant ethylene partial pressure of 1 bar, atemperature of 80° C. and a stirring speed of 1,500 rpm in the presenceof an industrial Ziegler-Natta catalyst based on Ti/MgCl₂ having a 1% Ticontent and the compound of Example 1 as cocatalyst.

At a ratio Ti:Al of 1:40-1:50, the catalyst system has a constantactivity of 30-50 kg polyethylene/g Ti.h.bar C₂ H₄.

What is claimed is:
 1. A coordination Catalyst system based ontransition metal compounds of subgroup IV to VIII and a cyclicorganometallic compound of main group III of the Periodic Table ofElements, wherein said cyclic organometallic compound is a compound ofthe formulae I or II ##STR3## in which M is B, Al, Ga, In,X¹, X², X³are, in each case independently of one another, CHR¹, NR², O, S, Y¹, Y²are, in each case independently of one another, --(CH₂)_(m) --,o-(CH₂)_(p) --C₆ H₄ --(CH₂)_(q) --, o-(CH₂)_(p) --C₆ H₆ --(CH₂)_(q) --,o-(CH₂)_(p) --C₆ H₈ --(CH₂)_(q) --, o-(CH₂)_(p) --C₆ H₁₀ --(CH₂)_(q) --,o-(CH₂)_(p) --C₅ H₄ --(CH₂)_(q) --, o-(CH₂)_(p) --C₅ H₆ --(CH₂)_(q) --,o-(CH₂)_(p) --C₅ H₈ --(CH₂)_(q) --, --(CH₂)_(p) --CH═CH--(CH₂)_(q) --, Zis NR³ R⁴, PR³ R⁴ , OR⁵, SR⁵, R¹ is H, OH, halogen, C₁₋₆ -alkyl or C₁₋₆-alkoxyl, C₅₋₇ -cycloalkyl, phenyl, R², R³, R⁴, R⁵ are, in each caseindependently of one another, H or C₁₋₆ -alkyl, C₅₋₇ -cycloalkyl,phenyl, R³ and R⁴ together also a C₄₋₆ -alkylene bridge, m is a numberfrom 1 to 6, p, q are, in each case independently of one another, anumber from 0 to 2, ##STR4## having M, R² and R³ as defined above and inwhich Z' is N, P, a is a number from 2 to 4, b, c are the numbers 0 or 1with b+c=1.
 2. A process for preparing polymers by coordinationpolymerization of alkenes and/or alkynes, comprising subjecting toeffective conditions a feed stream containing said alkenes and/oralkynes in the presence of a coordination catalyst system according toclaim
 1. 3. A coordination catalyst system according to claim 1, whereinX³ is --CH₂ --, O--, --S-- or an amino group optionally substituted byC₁₋₆ -alkyl, C₅₋₇ -cycloalkyl or phenyl.
 4. A coordination catalystsystem according to claim 1, wherein Y² is --(CH₂)_(n) -- and m is 1-6.5. A coordination catalyst system according to claim 1, wherein Y² is--(CH₂)_(p) --CH═CH═(CH₂)_(q) --, in which the double bond has a cisconfiguration.
 6. A coordination catalyst system according to claim 1,wherein in formula II, b is zero, and R² and R³ are each independentlyH, C₁₋₆ -alkyl, C₅₋₇ -cycloalkyl or phenyl.
 7. A coordination catalystsystem according to claim 1, wherein the compound of formula Iis1-Alumina-1-(4-dimethylaminobutyl)cyclobutane,1-Alumina-1-(2-dimethylaminoethyl)cyclopentane,1-Alumina-1-(2-diethylaminoethyl)cyclopentane,1-Alumina-1-(2-dipropylaminoethyl)cyclopentane,1-Alumina-1-(2-diisopropylaminoethyl)cyclopentane,1-Alumina-1-(2-dibutylaminoethyl)cyclopentane,1-Alumina-1-(3-dimethylaminopropyl)cyclopentane,1-Alumina-1-(3-diethylaminopropyl)cyclopentane,1-Alumina-1-(3-dipropylaminopropyl)cyclopentane,1-Alumina-1-(3-diisopropylaminopropyl)cyclopentane,1-Alumina-1-(3-dibutylaminopropyl)cyclopentane,1-Alumina-1-(4-dimethylaminobutyl)cyclopentane,1-Alumina-1-(4-diethylaminobutyl)cyclopentane,1-Alumina-1-(4-dipropylaminobutyl)cyclopentane,1-Alumina-1-(4-diisopropylaminobutyl)cyclopentane,1-Alumina-1-(4-dibutylaminobutyl)cyclopentane,1-Alumina-1-(3-dimetylaminopropyl)-2-methylcyclopentane,1-Alumina-1-(2-dimethylaminoethyl)cyclohexane,1-Alumina-1-(2-diethylaminoethyl)cyclohexane,1-Alumina-1-(2-dipropylaminoethyl)cyclohexane,1-Alumina-1-(2-diisopropylaminoethyl)cyclohexane,1-Alumina-1-(2-dibutylaminoethyl)cyclohexane,1-Alumina-1-(3-dimethylaminopropyl)cyclohexane,1-Alumina-1-(3-diethylaminopropyl)cyclohexane,1-Alumina-1-(3-dipropylaminopropyl)cyclohexane,1-Alumina-1-(3-diisopropylaminopropyl)cyclohexane,1-Alumina-1-(3-dibutylaminopropyl)cyclohexane,1-Alumina-1-(4-dimethylaminobutyl)cyclohexane,1-Alumina-1-(4-diethylaminobutyl)cyclohexane,1-Alumina-1-(4-dipropylaminobutyl)cyclohexane,1-Alumina-1-(4-diisopropylaminobutyl)cyclohexane,1-Alumina-1-(4-dibutylaminobutyl)cyclohexane,1-Alumina-1-(o-diethylaminobenzyl)cyclopentane,1-Alumina-1-(o-diethylaminobenzyl)cyclohexane,1-Alumina-1-(o-diisopropylaminobenzyl)cyclohexane,1-Alumina-1-(2-o-dimethylaminophenylethyl)cyclopentane,1-Alumina-1-(2-o-diethylaminophenylethyl)cyclobutane,1-Galla-1-(3-dimethylaminopropyl)cyclobutane,1-Galla-1-(2-dimethylaminoethyl)cyclopentane,1-Galla-1-(3-dimethylaminopropyl)cyclopentane,1-Galla-1-(2-dimethylaminoethyl)cyclopentane,1-Galla-1-(2-diethylaminoethyl)cyclopentane,1-Galla-1-(2-dipropylaminoethyl)cyclopentane,1-Galla-1-(2-diisopropylaminoethyl)cyclopentane,1-Galla-1-(2-dibutylaminoethyl)cyclopentane,1-Galla-1-(3-diethylaminopropyl)cyclopentane,1-Galla-1-(3-dipropylaminopropyl)cyclopentane,1-Galla-1-(3-diisopropylaminopropyl)cyclopentane,1-Galla-1-(3-dibutylaminopropyl)cyclopentane,1-Galla-1-(4-dimethylaminobutyl)cyclopentane,1-Galla-1-(4-diethylaminobutyl)cyclopentane,1-Galla-1-(4-dipropylaminobutyl)cyclopentane,1-Galla-1-(4-isopropylaminobutyl)cyclopentane,1-Galla-1-(4-dibutylaminobutyl)cyclopentane,1-Galla-1-(3-dimethylaminopropyl)cyclohexane,1-Galla-1-(3-diethylaminopropyl)cyclohexane,1-Galla-1-(3-dipropylaminopropyl)cyclohexane,1-Galla-1-(3-diisopropylaminopropyl)cyclohexane,1-Galla-1-(3-dibutylaminopropyl)cyclohexane,1-Galla-1-(2-dimethylaminoethyl)cyclohexane,1-Galla-1-(2-diethylaminoethyl)cyclohexane,1-Galla-1-(2-dipropylaminoethyl)cyclohexane,1-Galla-1-(2-diisopropylaminoethyl)cyclohexane,1-Galla-1-(2-dibutylaminoethyl)cyclohexane,1-Galla-1-(4-dimethylaminobutyl)cyclohexane,1-Galla-1-(4-diethylaminobutyl)cyclohexane,1-Galla-1-(4-dipropylaminobutyl)cyclohexane,1-Galla-1-(4-isopropylaminobutyl)cyclohexane,1-Galla-1-(4-dibutylaminobutyl)cyclohexane,1-Galla-1-(o-dimethylaminobenzyl)cyclobutane,1-Galla-1-(o-dimethylaminobenzyl)cyclopentane,1-Galla-1-(o-dimethylaminobenzyl)cyclohexane,1-Galla-1-(o-diethylaminobenzyl)cyclohexane,1-Galla-1-(o-dipropylaminobenzyl)cycloheptane,1-Inda-1-(2-diethylaminoethyl)cyclobutane,1-Inda-1-(2-dimethylaminoethyl)cyclopentane,1-Inda-1-(2-diethylaminoethyl)cyclopentane,1-Inda-1-(2-dipropylaminoethyl)cyclopentane,1-Inda-1-(2-diisopropylaminoethyl)cyclopentane,1-Inda-1-(2-dibutylaminoethyl)cyclopentane,1-Inda-1-(3-dimethylaminopropyl)cyclopentane,1-Inda-1-(3-diethylaminopropyl)cyclopentane,1-Inda-1-(3-dipropylaminopropyl)cyclopentane,1-Inda-1-(3-diisopropylaminopropyl)cyclopentane,1-Inda-1-(3-dibutylaminopropyl)cyclopentane,1-Inda-1-(4-dimethylaminobutyl)cyclopentane,1-Inda-1-(4-diethylaminobutyl)cyclopentane,1-Inda-1-(4-dipropylaminobutyl)cyclopentane,1-Inda-1-(4-diisopropylaminobutyl)cyclopentane,1-Inda-1-(4-dibutylaminobutyl)cyclopentane,1-Inda-1-(2-dimethylaminoethyl)cyclohexane,1-Inda-1-(2-diethylaminoethyl)cyclohexane,1-Inda-1-(2-dipropylaminoethyl)cyclohexane,1-Inda-1-(2-diisopropylaminoethyl)cyclohexane,1-Inda-1-(2-dibutylaminoethyl)cyclohexane,1-Inda-1-(3-dimethylaminopropyl)cyclohexane,1-Inda-1-(3-diethylaminopropyl)cyclohexane,1-Inda-1-(3-dipropylaminopropyl)cyclohexane,1-Inda-1-(3-diisopropylaminopropyl)cyclohexane,1-Inda-1-(3-dibutylaminopropyl)cyclohexane,1-Inda-1-(4-dimethylaminobutyl)cyclohexane,1-Inda-1-(4-diethylaminobutyl)cyclohexane,1-Inda-1-(4-dipropylaminobutyl)cyclohexane,1-Inda-1-(4-diisopropylaminobutyl)cyclohexane,1-Inda-1-(4-dibutylaminobutyl)cyclohexane,1-Inda-1-(o-diisopropylaminobenzyl)cyclobutane,1-Inda-1-(o-dimethylaminobenzyl)cyclopentane,1-Inda-1-(o-dibutylaminobenzyl)cyclopentane,1-Inda-1-(o-dimethylaminobenzyl)cyclohexane,1-Inda-1-(o-diethylaminobenzyl)cyclohexane,1-Inda-1-(o-dimethylaminobenzyl)cyclooctane,2,5-Dimethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1aluminacyclopentane,2,5-Dimethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-aluminacyclohexane,2,5-Dimethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-aluminacycloheptane,2,5-Dimethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-aluminacyclopentane,2,5-Dimethyl-1-(3-diethylaminopropyl)-2,5-diaza-1-aluminacyclohexane,2,5-Dimethyl-1-(3-diethylaminopropyl)-2,5-diaza-1-aluminacycloheptane,2,5-Diethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-aluminacyclohexane,2,5-Diethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-aluminacyclopentane,2.5-Diethyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-aluminacyclohexane,2,5-Diethyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-aluminacyclopentane,2,5-Diethyl-1-(4-dimethylaminobutyl) -2,5-diaza-1-aluminacycloheptane,2-Ethyl-5-propyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-aluminacyclohexane,2-Ethyl-5-propyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-aluminacyclopentane,2-Ethyl-5-propyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-aluminacycloheptane,2,5-Dimethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-gallacyclopentane,2,5-Dimethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-gallacyclohexane,2,5-Dimethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-gallacycloheptane,2,5-Dimethyl-1-(3-diethylaminopropyl)-2,5-diaza-1-gallacyclopentane,2,5-Dimethyl-1-(3-diethylaminopropyl)-2,5-diaza-1-gallacyclohexane,2,5-Dimethyl-1-(3-diethylaminopropyl)-2,5-diaza-1-gallacycloheptane,2,5-Diethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-gallacyclohexane,2,5-Diethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-gallacyclopentane,2,5-Diethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-gallacycloheptane,2,5-Diethyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-gallacyclohexane,2,5-Diethyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-gallacyclopentane,2,5-Diethyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-gallacycloheptane,2-Ethyl-5-propyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-gallacyclohexane,2-Ethyl-5-propyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-gallacyclopentane,2-Ethyl-5-propyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-gallacycloheptane,2,5-Dimethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-indacyclopentane,2,5-Dimethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-indacyclohexane,2,5-Dimethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-indacycloheptane,2,5-Dimethyl-1-(3-diethylaminopropyl)-2,5-diaza-1-indacyclopentane,2,5-Dimethyl-1-(3-diethylaminopropyl)-2,5-diaza-1-indacyclohexane,2,5-Dimethyl-1-(3-diethylaminopropyl)-2,5-diaza-1-indacycloheptane,2,5-Diethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-indacyclohexane,2,5-Diethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-indacyclopentane,2,5-Diethyl-1-(3-dimethylaminopropyl)-2,5-diaza-1-indacycloheptane,2,5-Diethyl-1-(3-dimethylaminobutyl)-2,5-diaza-1-indacyclohexane,2,5-Diethyl-1-(3-dimethylaminobutyl)-2,5-diaza-1-indacyclopentane,2,5-Diethyl-1-(3-dimethylaminobutyl)-2,5-diaza-1-indacycloheptane,2-Ethyl-5-propyl-1-(4-dimethylaminobutyl)-2,5-diaza-1indacyclohexane,2-Ethyl-5-propyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-indacyclopentaneor2-Ethyl-5-propyl-1-(4-dimethylaminobutyl)-2,5-diaza-1-indacycloheptane.8. A catalyst system according to claim 1, wherein the compound offormula II is5-Methyl-1-galla-5-azacyclooctane,1,5-Dimethyl-1-galla-5-azacyclooctane,1,5-Diethyl-1-galla-5-azacyclooctane,1,5-Dipropyl-1-galla-5-azacyclooctane,1,5-Dimethyl-1-alumina-5-azacyclooctane,1,5-Diethyl-1-alumina-5-azacyclooctane,1,5-Diisopropyl-1-alumina-5-azacyclooctane,1,5-Dibutyl-1-alumina-5-azacyclooctane,1-Methyl-5-ethyl-1-galla-5-azacyclooctane,1-Ethyl-5-methyl-1-alumina-5-azacyclooctane,1,6-Dimethyl-1-galla-6-azacyclodecane,1,6-Dimethyl-1-alumina-6-azacyclodecane,1,6-Diethyl-1-galla-6-azacyclodecane,1,4-Dimethyl-1-galla-4-azacyclohexane,1,6-Diethyl-1-alumina-6-azacyclodecane,1-Galla-5-azabicyclo[3.3.3]undecane, 1-Galla-4-azabicyclo[2.2.2]octane,1-Alumina-5-azabicyclo[3.3.3]undecane,1-Alumina-4-azabicyclo[2.2.2]octane,1-Galla-6-azabicyclo[4.4.4]tetradecane,1-Alumina-6-azabicyclo[4.4.4]tetradecane,1,5-Dimethyl-1-inda-5-azacyclooctane,1,5-Diethyl-1-inda-5-azacyclooctane,1,5-Dipropyl-1-inda-5-azacyclooctane,1,5-Diisopropyl-1-inda-5-azacyclooctane,1,5-Dibutyl-1-inda-5-azacyclooctane,1-Methyl-5-ethyl-1-inda-5-azacyclooctane,1-Ethyl-5-propyl-1-inda-5-azacyclooctane,1,6-Dimethyl-1-inda-6-azacyclodecane,1,6-Diethyl-1-inda-6-azacyclodecane,1,4-Dimethyl-1-inda-4-azacyclohexane,1-Inda-5-azabicyclo[3.3.3]undecane, 1-Inda-4-azabicyclo[2.2.2]octane,1-Methyl-5-cyclohexyl-1-inda-5-azacyclooctane,1-Methyl-5-phenyl-1-inda-5-azacyclooctane,1-Inda-6-azabicyclo[4.4.4]tetradecane,1,6-Dimethyl-1-galla-6-azacyclodecane,1,6-Diethyl-1-galla-6-azacyclodecane,1,6-Dipropyl-1-galla-6-azacyclodecane,1,6-Diisopropyl-1-galla-6-azacyclodecane,1,6-Dibutyl-1-galla-6-azacyclodecane,1,6-Di-tert-butyl-1-galla-6-azacyclodecane,1,6-Diisobutyl-1-galla-6-azacyclodecane,1,4-Dimethyl-1-galla-4-azacyclohexane,1,4-Diethyl-1-galla-4-azacyclohexane,1,4-Dipropyl-1-galla-4-azacyclohexane,1,4-Diisopropyl-1-galla-4-azacyclohexane,1,4-Dibutyl-1-galla-4-azacyclohexane,1,4-Diisobutyl-1-galla-4-azacyclohexane,1,4-Di-tert-butyl-1-galla-4-azacyclohexane,1-Methyl-5-ethyl-1-galla-5-azacyclooctane,1-Methyl-5-propyl-1-galla-5-azacyclooctane,1-Propyl-5-methyl-1-galla-5-azacyclooctane,1-Ethyl-5-methyl-1-galla-5-azacyclooctane,1-Ethyl-6-propyl-1-galla-6-azacyclodecane,1-Propyl-6-butyl-1-galla-6-azacyclodecane,1-Methyl-6-ethyl-1-galla-6-azacyclodecane,1-Methyl-4-ethyl-1-galla-4-azacyclohexane,1-Propyl-4-methyl-1-galla-4-azacyclohexane, or1-Ethyl-4-butyl-1-galla-4-azacyclohexane, substituted by C₁₋₆ -alkyl,C₅₋₇ -cycloalkyl or phenyl.
 9. A coordination catalyst system accordingto claim 1, wherein the compound of formula I or II is an organoaluminumcompound.
 10. A coordination catalyst according to claim 9, wherein theorganoaluminum compound is1-alumina-1-(3-dimethylaminopropyl)cyclohexane or1,5-dimethyl-1-alumina-5-azacyclooctane.
 11. A process according toclaim 2, wherein the alkenes are styrene, vinyl monomers or acrylic acidmonomers.